Sialon cutting tool composition

ABSTRACT

A sialon ceramic material comprising a ceramic core selected from alpha-prime-sialon, beta-prime-sialon, and an intergranular phase and, optionally substantially substantially inert refractory phases. The sialon ceramic material has an alloyed surface layer with a substantially increased aluminum and oxygen content.

This is a continuation of co-pending application Ser. No. 051,964 filed on May 19, 1977, now abandoned.

BACKGROUND OF THE INVENTION

Materials for cutting tool inserts fall into several well-known categories. These include high speed steels, cast alloys of cobalt and chromium, sintered carbides and ceramic materials. Each type of material has an advantage depending upon the application. Ceramic materials are used in especially difficult applications. They have high hardness, chemical inertness and wear resistance even at elevated temperatures. However, ceramic cutting tools are often deficient in toughness.

There has been a growing interest in the use of ceramic materials known in the art as sialons as materials for cutting tools. Sialons are compositions of silicon, aluminum, oxygen and nitrogen and sometimes other elements. Several sialon phases are recognized including alpha-prime-sialon and beta-prime-sialon. Cutting tools may be made from either alpha-prime-sialons, beta-prime-sialons or mixtures thereof. As with many ceramic compositions, sialons often comprise an intergranular phase. For a description of a beta-prime-sialon material, reference is made to U.S. Pat. No. 4,127,416. For a complete description of mixed alpha-prime-sialon/beta-prime-sialon compositions useful for cutting tool inserts, reference is made to U.S. Pat. Nos. 4,563,433 and 4,547,470.

One advantage of sialon ceramic cutting tool inserts is increased toughness. For a ceramic material, sialons have exceptional toughness. Sialons have higher hot hardness and elevated temperature compressive strength than cemented carbides. This should allow sialons to resist thermal deformation and flank wear during machining better than cemented carbides. A disadvantage of sialon cutting tool inserts is that they have less than desired chemical resistance. Under the conditions of high speed steel roughing, both sialons and cemented carbides will quickly fail by crater wear due to the affinity between these materials and hot steel chips.

It has been suggested that sialon cutting tools be provided with a chemical and abrasion resistant coating applied by chemical vapor deposition. For example, in U.S. Pat. No. 4,539,251, it was taught to provide sialon compositions with a coating of a carbide of Ti, Zr, or Hf, nitride thereof, carbo-nitride thereof, carbo-oxide thereof, and carbo-nitro-oxide thereof. It is further taught in this patent that an alumina coating may be placed over the above described coating, but no suggestion is made to place the alumina coating directly upon the sialon.

Applicants have attempted to place an alumina coating directly upon sialon compositions by chemical vapor deposition in order to significantly retard the chemical reaction with the hot steel chips. However, two problems were discovered that made the use of an alumina coating applied by chemical vapor deposition impractical. Devitrification of the intergranular glass phase occurred producing a B-phase (Y₂ SiAlO₅ N) which results in a substantially lower toughness of the substrate. Also, the intergranular phase near the surface escaped, leaving porosity behind in about a ten micron thick surface layer adjacent to the coatings. The degradation in the substrate properties resulted in a tendency for edge chipping and fracture during metal cutting, although flank water and crater wear resistances were better than coated cemented carbide tool inserts tested under the same conditions.

The problem of degradation during chemical vapor deposition is related at least in part to the temperature of the substrate during the process. The applicants have determined that simply heating sialon ceramic materials (either the beta-prime-sialon type or the alpha-prime-sialon/beta-prime-sialon type) to 1000 degrees Centigrade for the period of time it normally takes to deposit an alumina coating results in a drop in fracture toughness.

In seeking ways to restore the toughness of alumina coated sialon cutting inserts, applicants have discovered a surface alloyed sialon material that has the toughness of virgin sialon and substantially improved chemical and wear resistance.

SUMMARY OF THE INVENTION

It is an advantage of this invention to provide a method of surface alloying a sialon composition to provide a sialon layer at the surface with an increased aluminum and oxygen content.

It is a further advantage of the herein described invention to provide a sialon ceramic cutting tool insert that has excellent fracture toughness and improved chemical inertness.

Briefly, according to this invention, there is provided a method of alloying the surface of sialon materials to increase the Z value of the beta-prime-sialons near the surface comprising the steps of (a) preparing a sialon core composition; (b) applying a coating of alumina to the surface of the core composition in a thickness of about 1 to 10 microns by chemical vapor deposition; and (c) heat treating the coated composition in a non-oxidizing atmosphere at temperatures and pressures and for times until at least a portion of the alumina coating diffuses into the surface of the core composition. Preferably, at least one-half of the volume of the alumina coating diffuses into the surface of the core composition. The sialon core composition consists essentially of alpha-prime-sialon and/or beta-prime-sialon, and permissively, an intergranular phase and, optionally, substantially inert refractory phases. The refractory phases are selected from the group consisting of refractory oxides, carbides, and nitrides of metals, and mixtures, compounds and solid solutions thereof. Preferably, the chemical vapor deposition of the alumina coating is made at temperatures between 800 and 1100 degrees Centigrade, and most preferably, the chemical vapor deposition of the alumina coating is made at temperatures between 950 and 1050 degrees Centigrade. The thickness of the alumina coating applied by chemical vapor deposition is between 1 and 10 microns, preferably 5 to 7 microns.

The heat treating conditions suitable for preparing materials according to this invention are set forth in the following table:

    ______________________________________                                         Condition   Useful Range  Preferred Range                                      ______________________________________                                         Temperature 1300-1800° C.                                                                         1500-1700° C.                                 Pressure    up to 30 ksi  up to 30 ksi                                         Time        15 min. to 5 hours                                                                           about 1 hour                                         Atmosphere  N.sub.2, Ar, He                                                                              N.sub.2                                              ______________________________________                                    

Where pressure is applied, it is preferably applied by hot isostatic pressing. The times and temperatures are, of course, related to each other and furnace load. The higher the temperature, the shorter the time required. The larger the furnace load, the longer the time. The precise heat treating conditions are those that will permit the aluminum and oxygen in the alumina coating to diffuse into the sialon surface and to cover the loss of toughness that takes place during the chemical vapor deposition process. In one embodiment, the times and temperatures are selected to cause only a portion of the aluminum and oxygen to diffuse into the sialon workpiece leaving a portion of the alumina on the surface as alpha alumina. With heat treating at lower temperatures and shorter times, it is more likely alumina will be left upon the surface after heat treatment. With even lower temperatures and/or even shorter times, the thickness of the alumina coating will increase.

According to one specific embodiment, the core composition consists essentially of a matrix of beta-prime-sialon of 0.1 to 10 volume percent intergranular phase. According to yet another specific embodiment, the core composition consists essentially of a matrix of up to 70 volume percent alpha-prime-sialon, 10 to 99.9 percent volume beta-prime-sialon and up to 10 percent of an intergranular phase. A variation of these embodiments would be similar compositions having a substantially inert refractory phase distributed in the matrix. According to still yet another specific embodiment, the sialons in the core composition have a volume ratio of alpha-prime-sialon to beta-prime-sialon between 5:95 and 95:5.

Generally, the intergranular phase will comprise a glassy or crystalline phase from the group YAG, N-YAM, Y-N-alpha-wollastonite, B-phase, N-apatite, N-melilite and glass.

The substantially inert refractory phases may comprise phases such as titanium nitride which are dispersed within the sialon matrix of the core composition. During manufacture of the core, they are mixed with the sialon forming ingredients as a fine powder. The substantially inert refractory phase may be present in amounts up to 80 volume percent. The refractory phases are called substantially inert because there is little reaction between them and the sialon matrix phase.

In addition to the method, there is provided according to this invention, a new sialon ceramic material useful, for example, for cutting tools, comprising a ceramic core consisting essentially of alpha-prime-sialon and/or beta-prime-sialon, and, permissively an intergranular phase and, optionally, substantially inert refractory phases, said sialon ceramic material having an alloyed surface layer having a substantially increased aluminum and oxygen content as compared with the core composition. The beta-prime-sialon phase in the core comprises a lower Z sialon than the beta-prime-sialon phase in the alloyed surface layer. Preferably, the alloyed surface layer is approximately 2 to 10 microns thick. Most preferably, the porosity of the surface layer is equal to the porosity of the core. It is especially preferred that a small amount of alumina remain upon the surface of the material or cutting tools.

In a specific preferred embodiment, the beta-prime-sialon phase of the core material has a Z value greater than 0 and less than or equal to 2 and the beta-prime-sialon phase of the alloyed surface layer has a Z value greater than that of the core material and less than or equal to 4. The Z value of a beta-prime-sialon is defined by the following formula:

    Si.sub.6-Z Al.sub.Z O.sub.Z O.sub.Z N.sub.8-Z

According to a special method embodiment of this invention, a method is provided for alloying the surface of the sialon workpieces to increase the aluminum and oxygen content and for providing an outer coating over the alloyed surface comprising a refractory coating composition being carbides, nitrides, carbo-nitrides, oxides or mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium. This method comprises first applying an alumina coating to the surface of the sialon core composition by chemical vapor deposition and then applying the refractory coating composition by chemical vapor deposition over the alumina coating. The heat treatment step is controlled so that at least a substantial portion of the alumina and oxygen of the alumina coating diffuses into the core composition but heat treatment is discontinued while at least a portion of the outer refractory coating retains its chemical integrity. Specifically, if the outer refractory coating is titanium nitride, then the heat treatment is preferably discontinued while a small layer of alumina may be found between the alloyed surface of the core composition and the titanium nitride coating. This special method embodiment results in a new sialon ceramic material comprising a sialon ceramic core having an alloyed layer of higher aluminum and oxygen content and an adjacent refractory surface layer or coating which comprises carbides, nitrides, carbo-nitrides, oxides or mixtures of vanadium, titanium, tantalum, niobium, hafnium or zirconium.

BRIEF DESCRIPTION OF THE DRAWINGS

Further features and other objects and advantages will become clear from the following description made with reference to the drawings in which:

FIG. 1 is a bar graph comparing Vickers hardness (18.5 kg loads) (GPa) of an alpha-prime-sialon/beta-prime-sialon cutting tool composition (KYON 2000)¹ and a beta-prime-sialon cutting tool composition (KYON 3000) as received, after application of an alumina coating by chemical vapor decomposition and after surface alloying according to this invention.

FIG. 2 is a bar graph comparing the Palmqvist fracture toughness, (18.5 kg loads) (kg/mm) of the sialon compositions referred to in FIG. 1 as received, after application of an alumina coating and after surface alloying.

FIG. 3 is a bar graph comparing tool-lives (minutes) and failure modes of a cemented carbide (KC950 Kennametal Grade), a two-phase ceramic composition comprising alumina and titanium carbide (KO90 Kennametal Grade) and two surface alloyed sialon compositions according to this invention; specifically, an alpha-prime-sialon/beta-prime-sialon composition (KYON 2000) and a beta-prime-sialon composition (KYON 3000) in high speed roughing of low alloy steel (4340).

FIG. 4 is a bar graph comparing tool-lives (minutes) and failure modes of a cemented carbide (KC950), a two-phase ceramic composition comprising alumina and titanium carbide (K090) and two surface alloyed sialon compositions according to this invention; specifically, an alpha-prime-sialon/beta-prime-sialon composition (KYON 2000) and a beta-prime-sialon composition (KYON 3000) in high speed roughing of medium carbon steel (1045).

DETAILED DESCRIPTION OF THE INVENTION EXAMPLES I AND II

Specimens of a commercially available alpha-prime-sialon/beta-prime-sialon composition previously used for cutting tool applications (KYON 2000) and specimens of another commercially available beta-prime-sialon material also previously used for cutting tool applications (KYON 3000) were coated by chemical vapor deposition at 950 degrees Centigrade for a time long enough to build up an alumina coating between 5 and 7 microns thick. The specimens had previously been manufactured by known processes, for example, as set forth in U.S. Pat. Nos. 4,563,433 and 3,991,166. (The coatings for the examples being described were applied to previously sintered and densified specimens; however, applicants contemplate that the coatings could be applied to specimens that have been sintered but not yet fully densified by hot isostatic pressing. Where the specimens have to be densified by uniaxial hot pressing in graphite molds, the coating normally would follow the densification by hot pressing and shaping by grinding.) The coated specimens were then heat treated at 1750 degrees Centigrade in helium at 20 ksi. The heat treatment (in this case by hot isostatic pressing) resulted in significant interdiffusion between the alumina coating and the substrate or core specimen.

Properties of the specimens of Example I (KYON 2000) and Example II (KYON 3000) as received, with a 6 micron alumina coating and with surface alloying according to this invention are set forth in Tables 1 and 2, respectively.

                  TABLE 1                                                          ______________________________________                                                   EXAMPLE I                                                                        AS                    HEAT                                         PROPERTY    RECEIVED   COATED     TREATED                                      ______________________________________                                         Density (g/cc):                                                                            3.269      3.277      3.275                                        Vickers     15.50 ± .22                                                                            15.67 ± .24                                                                            15.84 ± .20                               Hardness - 18.5 kg                                                             (GPa):                                                                         Fracture Tough-                                                                            37.17 ± .99                                                                            35.11 ± 2.06                                                                           39.08 ± .39                               ness - 18.5 kg                                                                 Palmqvist                                                                      W (kg/mm):                                                                     K.sub.1C-  (MPam.sup.1/2).sup.2 :                                                          6.51 ± .11                                                                             6.26 ± .25                                                                             6.72 ± .04                                X-ray Diffraction:                                                                         β', α', *                                                                      β', α', *                                                                      β', α', *                         of core                                                                        ______________________________________                                          * = Very low N--Apatite or N--YAM                                        

                  TABLE 2                                                          ______________________________________                                                   EXAMPLE II                                                                       AS                    HEAT                                         PROPERTY    RECEIVED   COATED     TREATED                                      ______________________________________                                         Density (g/cc):                                                                            3.248      3.183      3.213                                        Vickers     14,75 ± .18                                                                            14.23 ± .36                                                                            14.76 ± .13                               Hardness - 18.5 kg                                                             (GPa):                                                                         Fracture Tough-                                                                            42.91 ± .54                                                                            32.81 ± 2.93                                                                           44.95 ± 2.63                              ness - 18.5 kg                                                                 Palmqvist                                                                      W (kg/mm):                                                                     K.sub.1C- (MPam.sup.1/2)                                                                   7.02 ± .04                                                                             5.96 ± .38                                                                             7.16 ± .17                                X-ray Diffraction:                                                                         β', B β', B β'                                      of core                                                                        ______________________________________                                          B = Bphase                                                                     .sup.2 K.sub.1C was determined in accordance with Evans and Charles,           "Fracture Toughness Determinations by Indentation," J. Am. Ceramic             Society, Vol. 59, No. 7-8, P. 731.                                       

Selected data from Tables 1 and 2 are set forth in FIGS. 1 and 2. With reference to FIG. 1, it can be seen that hardness of the substrate is only slightly affected by a chemical vapor deposition coating and is somewhat improved by surface alloying, i.e., coating followed by hot isostatic pressing. With reference to FIG. 2, it is quite clear that coating alone has a pronounced detrimental effect on fracture toughness, but that surface alloying measurably improves fracture toughness. Fracture toughness of KYON 3000 appears to be much more sensitive to the coating and hot isostatic pressing treatments compared to KYON 2000.

X-ray diffraction data on the surface alloyed samples showed no distinct alumina phase and no new phases as compared with the as-received sialon materials. The B-phase was not detected in the KYON 3000 after the hot isostatic pressing.

Metal Cutting Tests

High speed steel roughing is the intended application of coated sialon tool inserts. Metal cutting tests were conducted on Examples I and II under the following conditions representing high speed steel roughing applications:

    ______________________________________                                         Workpieces:     1045 Steel                                                                     4340 Steel                                                     Speed:          1000 surface feet per                                                          minute (sfm)                                                   Feed:           0.025 inches per revolution                                                    (ipr)                                                          Depth of Cut:   0.l5 inch                                                      Insert Style:   SNG - 433                                                      ______________________________________                                          1045 is a medium carbon steel and 4340 is a low alloy steel.             

The results of the metal cutting tests for Examples I and II are shown in FIGS. 3 and 4. These are bar graphs wherein tool-life in minutes is reported along with the failure mode: NW=nose wear failure; FW=flank wear failure; CW=crater wear failure; BK=breakage failure and TD=thermal deformation failure. The surface alloyed sialon cutting tools were compared with a commercial cemented carbide tool (KC950) in a test with the low alloy steel. As shown in FIG. 3, both of the surface coated sialons have superior tool life, the sialon tools failing in the more predictable wear modes. The surface alloyed sialon cutting tools were compared to commercial cemented carbide tools (KC950) and commercial ceramic tools (KO90) in a test with medium carbon steel. The surface alloyed alpha-prime-sialon/beta-prime-sialon (KYON 2000) had decidedly superior service life failing in the more predictable wear modes. The beta-prime-sialon (KYON 3000) had adequate tool life compared to the cemented carbide and ceramic tools but certainly not as long. Failure, however was in the more predictable wear mode.

Stated another way, the surface alloyed KYON 2000 tool had almost twice the tool life of the cemented carbide tool with both steels.

Examples III-VII

A number of variations of Example I were investigated. In Example I and all the variations discussed in this section, the time at temperature during the heat treatment was one hour. Example III was similar to Example I except that the heat treatment was at 1100 degrees Centigrade at 20 ksi argon atmosphere (hot isostatic pressure). Example IV was similar to Example I except the heat treatment was 1600 degrees Centigrade at 15 psi (atmospheric pressure) in an argon atmosphere. Example V was similar to Example I except that the heat treatment was at 1600 degrees Centigrade at 20 ksi nitrogen atmosphere (hot isostatic pressure). Example VI was similar to Example I except that the heat treatment was at 1750 degrees Centigrade at 20 ksi nitrogen atmosphere (hot isostatic pressure). Example VII was similar to Example I except that heat treatment was at 1600 degrees Centigrade at 15 psi nitrogen (atmospheric pressure). The variation in hardness, toughness and surface composition for Examples III to VII are set forth in the following Table 3.

                  TABLE 3                                                          ______________________________________                                                  VICKERS    PALMQVIST    X-RAY DIF-                                             HARDNESS   TOUGHNESS    FRACTION                                      EXAMPLE  18.5 kg (GPa)                                                                             18.5 kgW (kg/mm)                                                                            OF SURFACE                                    ______________________________________                                         KYON 2000                                                                               15.50      37.17        beta prime,                                                                    alpha prime                                   KYON 2000                                                                               15.67      35.11        alumina,                                      (as coated)                      beta prime,                                                                    alpha prime                                   III      13.72      24.12        beta prime,                                                                    alumina, B--,                                                                  phase, alpha                                                                   prime, N--YAM                                 IV       16.11      35.22        beta prime,                                                                    alumina,                                                                       alpha prime,                                                                   N--melilite                                   V        16.06      37.55        beta prime,                                                                    alumina,                                                                       alpha prime                                   VI       16.10      37.27        beta prime,                                                                    alpha prime                                   VII      16.11      34.66        beta prime,                                                                    alumina,                                                                       alpha prime,                                                                   N--melilite                                   ______________________________________                                    

Example III shows that insufficient heat treatment (1100 degrees Centigrade) resulted in reduced hardness and toughness. Comparing Examples V and VII shows that hot isostatic pressing can result in improved toughness over heat treatment at atmospheric pressure at the same treatment temperatures. Comparison of Examples V and VI shows that increase in heat treating temperature can result in complete diffusion of the aluminum and oxygen of the alumina into the sialon surface leaving only the beta-prime-sialon and alpha-prime-sialon phases.

Examples VIII-IX

Examples VIII and IX were similar to Example I except that following the chemical vapor deposition of the alumina coating, an outer titanium nitride coating was applied also by chemical vapor deposition over the alumina coating. The heat treatment given Example VIII was one hour at 1750 degrees Centigrade in a 20 ksi nitrogen atmosphere. The heat treatment for Example IX was one hour at 1750 degrees Centigrade in a 20 ksi argon atmosphere. The titanium nitride coating was intact after the heat treatments and did not react with the sialon core.

Examples X-XI

Examples X and XI were similar to Example I except the heat treating comprised one hour at 1650 degrees Centigrade in 15 psi nitrogen and one hour at 1650 degrees Centigrade in 20 ksi nitrogen.

Metal Cutting Tests

Metal cutting tests were conducted on Examples VIII to XI under the following conditions:

    ______________________________________                                         Workpieces:           l045 steel                                               Speed:                1000 sfm                                                 Feed:                 .025 ipr                                                 Depth of Cut:         0.1 inch                                                 Insert Style:         SNG-453                                                  ______________________________________                                    

The results of the metal cutting tests are set forth in the following Table 4:

                  TABLE 4                                                          ______________________________________                                                         TOOL LIFE    FAILURE                                           EXAMPLE         (MINUTES)    MODE                                              ______________________________________                                         VIII            2.5          NW, DOCN                                          IX              2.4          FW, DOCN                                          X               4.4          FW, CH                                            XI              2.6          FW, CR                                            I               2.0          FW, CR                                            KYON 2000       <0.7         FW, CR                                            KYON 2000 (as coated)                                                                          1.0          FW, CR                                            ______________________________________                                    

The acronyms for the failure modes noted in Table 4 mean the following: FW=flank wear failure; CR=crater wear failure; CH=chipped; DOCN=depth of cut notch failure; and NW=nose wear failure.

The data in Table 4 establishes the substantial advantage of surface alloyed compositions according to this invention when used as cutting tool inserts. Examples VIII to XI all had tool life at least twice that of KYON 2000 and coated (but not surface alloyed) KYON 2000.

The applicants do not wish to be bound by any proposed theory but it now appears that the surface alloyed according to this invention has the effect of increasing the Z value in the beta-prime-sialon phase near the surface. Recall the beta-prime-sialon has the general formula Si_(6-Z) Al_(Z) _(O) _(Z) N_(8-Z).

Having thus described the invention with the detail and particularity required by the Patent Laws, what is desired protected by Letters Patent is set forth in the following claims. 

What is claimed is:
 1. A sialon ceramic material comprising a ceramic core containing beta-prime-sialon phase, and an intergranular phase and, said sialon ceramic material having a beta-prime-sialon alloyed surface layer phase comprising an alloy of the beta prime sialon phase in said ceramic core with a substantially increased aluminum and oxygen content compared to the beta-prime-sialon in said ceramic core and wherein said alloyed surface layer has a thickness of 2 to 10 microns and bonded directly on said alloyed surface layer is a coating of alumina.
 2. The material according to claim 1 wherein the beta-prime-sialon phase in said ceramic core comprises a lower Z sialon than the beta-prime-sialon alloyed surface layer phase.
 3. The material according to claim 1 wherein the ceramic core consists essentially of beta-prime-sialon and 0.1 to 10 volume percent intergranular phase.
 4. The material according to claim 1 wherein the ceramic core consists essentially of up to 70 volume percent alpha-prime-sialon, 10 to 99.9 volume percent beta-prime-sialon and 0.1 to 10 volume percent of said intergranular phase.
 5. The material according to claim 1 wherein the ceramic core further contains alpha-prime-sialon and the volume ratio of alpha-prime-sialon to beta-prime-sialon is between 5:95 and 95:5 in said ceramic core.
 6. The material according to claim 1 wherein the porosity of the beta-prime-sialon alloyed surface layer is equal to the porosity of the ceramic core.
 7. The material according to claim 1 wherein the beta-prime-sialon phase of the ceramic core material has a Z value greater than 0 and less than or equal to 2 and the beta-prime-sialon alloyed surface layer phase has a Z value greater than that of the beta-prime-sialon phase of said ceramic core and less than
 4. 8. The material according to claim 1 wherein said ceramic core further contains a substantially inert refractory phase selected from the group consisting of refractory oxides, carbides, and nitrides of metals, and mixtures, compounds and solid solutions thereof.
 9. The material according to claim 1 further comprising a refractory outer layer disposed over the coating of alumina and wherein said refractory layer is selected from the group consisting of carbides, nitrides, carbo-nitrides, oxides and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 10. A method of alloying the surface of sialon material to increase the Z value of the beta-prime-sialons near the surface comprising the steps of:(a) preparing a sialon core composition, (b) applying a coating of alumina to the surface of the core composition in a thickness of about 1 to 10 microns by chemical vapor deposition, and (c) heat treating the coated composition at temperatures up to 1750 degrees Centigrade and for times until at least a portion of the oxygen and aluminum of the alumina coating diffuses into the surface of the core composition.
 11. The method according to claim 10 wherein the core composition consists essentially of alpha-prime-sialon, beta-prime-sialon, an intergranular phase and, optionally, substantially refractory phases.
 12. The method according to claim 10 wherein the core composition consists essentially of beta-prime-sialon and 0.1 to 10 volume percent intergranular phase.
 13. The method according to claim 10 wherein the core composition consists essentially of up to 70 volume percent alpha-prime-sialon, 10 to 99.9 percent beta-prime-sialon and up to 10 percent of an intergranular phase.
 14. The method according to claim 10 wherein the sialons in the core composition have a volume ratio of alpha-prime-sialon to beta-prime sialon between 5:95 and 95:5.
 15. The method according to claim 11 wherein the refractory phase is selected from the group consisting of refractory oxides, carbides, and nitrides of metals, and mixtures, compounds and solid solutions thereof.
 16. The method according to claim 10 wherein the chemical vapor deposition of the alumina coating is made at temperatures between 800 and 1100 degrees Centigrade.
 17. The method according to claim 10 wherein the chemical vapor deposition of the alumina coating is made at room temperatures between 950 and 1050 degrees Centigrade.
 18. The method according to claim 10 wherein the thickness of the alumina coating applied by chemical vapor deposition is between 5 and 7 microns.
 19. The method according to claim 10 wherein the heat treating takes place at temperatures between 1500 and 1700 degrees Centigrade, at pressures up to 30 ksi, and for periods between 15 minutes and 5 hours in a non-oxidizing atmosphere.
 20. The method according to claim 10 wherein the heat treating takes place at temperatures between 1300 and 1800 degrees Centigrade, at pressures up to 30 ksi, and for periods between 15 minutes and 5 hours in a non-oxidizing atmosphere.
 21. The method according to claim 10 wherein the heat treating takes place under isostatic pressing conditions in an atmosphere selected from the gases nitrogen, helium, and argon and mixtures thereof.
 22. A method according to claim 10 wherein the heat treating is discontinued prior to the time all of the alumina has diffused into the surface of the core composition.
 23. A method according to claim 12 wherein an outer refractory coating is deposited by chemical vapor deposition over the alumina coating, said outer refractory coating selected from the group carbides, nitrides, carbo-nitrides, oxides and mixtures thereof of the vanadium, titanium, tantalum, niobium, hafnium or zirconium and said heat treating being discontinued prior to the time the outer refractory coating begins to substantially react with the alloyed surface of the core composition.
 24. A cutting tool insert comprising a ceramic core consisting essentially of alpha-prime-sialon, beta-prime-sialon, an intergranular phase, and said ceramic core having an alloyed surface layer having beta-prime-sialon with a substantially increased aluminum and oxygen content and alpha-prime-sialon, wherein said alloyed surface layer has a thickness of 2 to 10 microns, and bonded over and directly to said alloyed surface layer is a coating of alumina.
 25. A cutting tool insert comprising a ceramic core consisting essentially of beta-prime-sialon, an intergranular phase and, said sialon ceramic material having an alloyed surface layer having a composition similar to the said ceramic core but with a substantially increased aluminum and oxygen content, wherein said alloyed surface layer has a thickness of 2 to 10 microns, and bonded over and directly to said alloyed surface layer is a coating of alumina.
 26. The cutting tool insert according to claim 24 wherein said alloyed surface layer contains beta-prime-sialon having a Z value greater than the Z value of the beta-prime-sialon in said ceramic core, but no more than
 4. 27. The cutting tool insert according to claim 25 wherein said alloyed surface layer contains beta-prime-sialon having a Z value greater than the Z value of the beta-prime-sialon in said ceramic core, but no more than
 4. 28. The cutting tool insert according to claim 26 wherein the degree of porosity in said alloyed surface layer is the same as the degree of porosity in said ceramic core.
 29. The cutting tool insert according to claim 27 wherein the degree of porosity in said alloyed surface layer is the same as the degree of porosity in said ceramic core.
 30. The cutting tool insert according to claim 26 further comprising a refractory outer layer disposed over the alumina coating and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides, and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 31. The cutting tool insert according to claim 27 further comprising a refractory outer layer disposed over the alumina coating and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides, and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 32. The cutting tool insert according to claim 28 further comprising a refractory outer layer disposed over the alumina coating and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides, and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 33. The cutting tool insert according to claim 29 further comprising a refractory outer layer disposed over the alumina coating and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides, and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 34. A sialon ceramic material comprising a ceramic core containing beta-prime-sialon phase, and an intergranular phase and, said sialon ceramic material having a beta-prime-sialon alloyed surface layer phase comprising an alloy of the beta prime sialon phase in said ceramic core with a substantially increased aluminum and oxygen content compared to the beta-prime-sialon in said ceramic core.
 35. The material according to claim 34 wherein the beta-prime-sialon phase in said ceramic core comprises a lower Z sialon than the beta-prime-sialon alloyed surface layer phase and wherein said alloyed surface layer has a thickness of 2 to 10 microns.
 36. The material according to claim 34 wherein the ceramic core consists essentially of beta-prime-sialon and 0.1 to 10 volume percent intergranular phase.
 37. The material according to claim 34 wherein the ceramic core consists essentially of up to 70 volume percent alpha-prime-sialon, 10 to 99.9 volume percent beta-prime-sialon and 0.1 to 10 volume percent of said intergranular phase.
 38. The material according to claim 34 wherein the ceramic core further contains alpha-prime-sialon and the volume ratio of alpha-prime-sialon to beta-prime-sialon is between 5:95 and 95:5 in said ceramic core.
 39. The material according to claim 34 wherein the porosity of the beta-prime-sialon alloyed surface layer is equal to the porosity of the ceramic core.
 40. The material according to claim 34 wherein the beta-prime-sialon phase of the ceramic core material has a Z value greater than 0 and less than or equal to 2 and the beta-prime-sialon alloyed surface layer has a Z value greater than that of the beta-prime-sialon phase of said ceramic core and less than
 4. 41. The material according to claim 34 wherein said ceramic core further contains a substantially inert refractory phase selected from the group consisting of refractory oxides, carbides, and nitrides of metals, and mixtures, compounds and solid solutions thereof.
 42. The material according to claim 34 further comprising a refractory outer layer disposed over said alloyed surface layer and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 43. A cutting tool insert comprising a ceramic core consisting essentially of alpha-prime-sialon, beta-prime-sialon, an intergranular phase, and said ceramic core having an alloyed surface layer having beta-prime-sialon with a substantially increased aluminum and oxygen content and alpha-prime-sialon.
 44. A cutting tool insert comprising a ceramic core consisting essentially of beta-prime-sialon, an intergranular phase and, said sialon ceramic material having an alloyed surface layer having a composition similar to the said ceramic core but with a substantially increased aluminum and oxygen content.
 45. The cutting tool insert according to claim 43 wherein said alloyed surface layer contains beta-prime-sialon having a Z value greater than the Z value of the beta-prime-sialon in said ceramic core, but no more than 4 and wherein said alloyed surface layer has a thickness of 2 to 10 microns.
 46. The cutting tool insert according to claim 44 wherein said alloyed surface layer contains beta-prime-sialon having a Z value greater than the Z value of the beta-prime-sialon in said ceramic core, but no more than 4 and wherein said alloyed surface layer has a thickness of 2 to 10 microns.
 47. The cutting tool insert according to claim 45 wherein the degree of porosity in said alloyed surface layer is the same as the degree of porosity in said ceramic core.
 48. The cutting tool insert according to claim 46 wherein the degree of porosity in said alloyed surface layer is the same as the degree of porosity in said ceramic core.
 49. The cutting tool insert according to claim 45 further comprising a refractory outer layer disposed over said alloyed surface layer and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides, and mixtures thereof vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 50. The cutting tool insert according to claim 46 further comprising a refractory outer layer disposed over said alloyed surface layer and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides, and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 51. The cutting tool insert according to claim 47 further comprising a refractory outer layer disposed over said alloyed surface layer and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides, and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium.
 52. The cutting tool insert according to claim 46 further comprising a refractory outer layer disposed over said alloyed surface layer and wherein said refractory outer layer is selected from the group consisting of carbides, nitrides, carbonitrides, oxides, and mixtures thereof of vanadium, titanium, tantalum, niobium, hafnium or zirconium. 